Treatment compositions, apparatus and methods for modifying keratinous surfaces

ABSTRACT

A treatment composition for, among other things, treating human skin. These compositions are stable, particulate containing, printer compositions that have one or more particulate suspending agents. The suspending agents can be present in a concentration of from about 0.1% to about 5%, by weight. The particles in the particulate composition have a combined Particle Size Distribution D50 in the range of about 200 μm to about 500 μm, and preferably the compositions have a zeta potential of negative 20 or less, or greater than positive 20. The particulate suspending agent is preferably a polyacrylate composition, even more preferably sodium polyacrylate. The particles can be present in a concentration of from about 1% to about 30.0%, by weight, and preferably the particles in the particulate composition have a combined Particle Size Distribution D90 of less than about 1 μm. The particulate compositions may contain TiO 2  particles and a second particulate composition which is an iron oxide based colorant particulate composition, another colorant particulate composition, or both.

FIELD OF THE INVENTION

This invention relates to printable treatment compositions and anapparatus for applying compositions to skin, and other keratinoussurfaces. The compositions can modify color or structure of thekeratinous surface.

BACKGROUND OF THE INVENTION

Inkjet devices, particularly piezo electric and thermal, are common forboth personal and industrial printing purposes. Most commonly, suchdevices are found in consumer homes as a means to create high qualityprints and photos. In such applications the fluid inks that are commonlyused for jetting onto various types of white papers utilize molecularcolorants commonly known as dyes. Dyes have an advantage for suchsystems because they are typically more stable than pigment colorants.Pigmented, or particulate based colorants are challenging to stabilizein fluids used for jetting applications because such fluids typicallyrequire a very low fluid viscosity, most commonly less than 10centipoise. For formulations of such low viscosity any particulateshaving a specific gravity greater that of the fluid carrier will havethe tendency to settle over time, and this settling rate can bepredicted for Newtonian fluids by Stoke's Law. Pigments are frequentlyused for black inkjet inks as they can be more easily stabilized byincorporating particles that are small enough, typically less than 50nanometers, to be at least partially stabilized by Brownian motion.

If opacity, or hiding power, of the underlying substrate is a desirableproperty of the ink then particles of greater than 100 μm are typicallyrequired. More specifically, particles less than 100 μm are invisible tothe human eye. The maximum efficiency of coverage is typically seen inparticles greater than 200 μm. Thus these particles will be large enoughto be subject to Stokes Law. Furthermore, the material or composition ofthe particle is also very important as materials with higher refractiveindexes will have greater hiding power. The challenge then becomesfinding a high refractive index particle with a specific gravity asclose as possible to common fluid carriers, usually between 0.8 and 1.2.The options are very limited and the most commonly used opacifyingparticles that have a refractive index greater than 2.0 also have aspecific gravity greater than 2.0. In the case of titanium dioxide, theopacifier most commonly used in the paint industry, the specific gravityis 4.2, making it settle rapidly in low viscosity fluids.

For these reasons existing inks that contain high specific gravityparticles like titanium dioxide are designed to be able to be re-mixablewith some type of vigorous mixing, either automated or hand shaking.There are only a few examples of such inks in the marketplace, and theyare all designed for industrial applications. All existing examples aredelivered in a bladder type cartridge or directly from a jar/can. Anexample of a titanium dioxide containing white ink from Epson is theEPSON Ultrachrome® GSX White Ink Cartridge. This is used for commercialprinting applications and utilizes a solvent based formulation designedfor Piezo inkjet systems. The cartridge is designed with a large bladderreservoir containing the ink and requires weekly re-mixing by vigorousagitation. Another example is the Hewlett Packard Scitex white inkcartridge. This intended for use in HP Scitex series printers outfittedwith an optional Scitex White Ink Upgrade Kit. The upgrade kit containsan HP White Ink Homogenizer that automatically shakes the white inkcartridge daily to keep the ink pigments in suspension. Thus currentopacifying white ink cartridges are only available for industrial orcommercial applications and all are designed to contain the pigment inan open reservoir type delivery system so that they are able to bere-mixed through shaking. These industrial printer examples are simplynot compatible with consumer, in-home, hand held printing devices.

For example, attempts have been made at more precise, and localizedapplication of compositions that hide, or cover-up skin deviations.Handheld devices that are moved across the skin have been developed toapply skin treatment compositions to local defects. But these deviceshave been plagued by a variety or technical issues including thedifficulties associated with printing compositions that compriseparticles as discussed above.

Therefore, there exists a need for printer compositions that containparticulate matter which can be printed on human skin, paper or anyother surface. The particles must be reasonably stable in solution andeasily redistributed into the solution should they settle. The particlesmust be big enough to be visible, but not so big that they fall out ofsolution quickly. And the particulate containing inks should be thinenough to be used with current printer cartridge and nozzle technology.Preferably, these particulate containing ink compositions can be used inmethods and apparatuses that can quickly and precisely detect tonal andtextural defects on skin. Then with equal speed and precision, apply theparticulate containing ink compositions directly to the deviations.These compositions and apparatuses are defined by the present invention.

SUMMARY OF THE INVENTION

The present invention relates to a treatment composition for, amongother things, treating human skin. These compositions are stable,particulate containing, printer compositions that have one or moreparticulate suspending agents. The suspending agents can be present in aconcentration of from about 0.1% to about 5%, by weight. The particlesin the particulate composition have a combined Particle SizeDistribution D50 in the range of about 200 μm (nano meters) to about 500μm, and preferably the compositions have a zeta potential of negative 20or less, or greater than positive 20, preferably, negative 30 or less,or greater than 30. The particulate suspending agent is preferably apolyacrylate composition, even more preferably sodium polyacrylate. Theparticles can be present in a concentration of from about 1% to about30.0%, by weight, and preferably the particles in the particulatecomposition have a combined Particle Size Distribution D90 of less thanabout 1 μm (micro meter). The particulate compositions may contain TiO₂particles and a second particulate composition which is an iron oxidebased colorant particulate composition, another colorant particulatecomposition, or both.

Further, one or more humectants in a concentration of from about 1.0% toabout 50.0%, by weight; and, water may be provided. The treatmentcompositions of this invention are used in a printer device such aspiezo electric, thermal ink jet or other drop on demand printer. Theprinter can be a part of an applicator having an applicator head havingone or more applicator nozzles which may be in a linear array. Theapparatus further has a reservoir containing the treatment composition,a sensor, and a CPU. The sensor takes an image of at least 10 μm² ofskin, the CPU analyzes the image to calculate one or more localized Lvalues of individual pixels or group of pixels of the skin. Then the CPUcompares the local L value to a predetermined background L value toidentify skin deviations. A skin deviation occurs where the differencebetween the local L and the background L, ΔL_(M), is greater than apredetermined ΔL_(S) (where “M” refers to a measured ΔL and “S” refersto a set ΔL). Skin deviations are identified by this method and thentreated with a treatment composition.

The present invention solves many problems with prior devices andmethods. Specifically, printing an ink that lightens, rather thandarkens the surface being treated. Lightening typically requires TiO₂particles, or the like. Particle containing inks are typically not usedin printers because they settle and sometimes pack after settling. Thecompositions of the present invention either slow settling to anacceptable rate, reduce packing so that the particles are resuspendedeasily (for example by simply turning the cartridge over), or both.Thus, printers using the present treatment compositions can lightentonal variations on skin and other surfaces that benefit from a lighterink.

The current invention is intended to further optimize an opacifying inkcontaining titanium dioxide and iron oxides so that it can be reliablyused in consumer applications without the need for the vigorousagitation required of all the current opacifying ink examples designedfor commercial applications. The current invention solves for opacifyingink formulations that require very little agitation in order to maintainformula homogeneity over time, thus easing the burden on the consumer ofmaintaining consistent print quality.

Further the speed with which a skin deviation is found and identified iscritical because the applicator is continuously moving across the skin.The quicker the deviation is identified, the quicker the applicatornozzle, or nozzles can be activated. The quicker the nozzles areactivated the more likely the skin treatment composition will hit thedeviation precisely. This allows for the optimal coverage of thedeviation, and minimal coverage on the areas of natural skin that do notneed treatment. Thus, the simpler the detection algorithm is, thequicker and more precise the overall correction process is. This is asubstantial improvement over more complicated, slower and less preciseapparatuses and methods of the past.

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims particularly pointing outand distinctly claiming the present invention, it is believed the samewill be better understood from the following description taken inconjunction with the accompanying drawing in which:

FIG. 1 is a schematic representation of an analytical window accordingto the present invention wherein skin is analyzed according to themethods of the present invention;

FIG. 2 is a hand held apparatus according to the present invention;

FIG. 3 is an ink jet cartridge according to the present invention;

FIG. 4 is the natural, uncovered skin of a female consumer;

FIG. 5 is the same female consumer in FIG. 4 with applied makeup;

FIG. 6 is the same female consumer as shown in FIG. 4, with no makeupon, after being treated by the methods and apparatuses of the presentinvention;

FIG. 7 is a cartridge assembly according to the present inventionshowing a possible placement position for a treatment compositiondispersing device,

FIG. 8 is a cartridge assembly according to the present inventionshowing an alternate form of a treatment composition pressure elementand treatment composition dispersing device;

FIGS. 9 and 10 are two views of the standpipe within a cartridge body;and

FIGS. 11 and 12 are two views of the standpipe within a cartridge body.

FIG. 13 is a graphical representation of the data in Table 3 for theZeta Potential v. pH of Particle 1;

FIG. 14 is a graphical representation of the data in Table 4 for theZeta Potential v. pH of Particle 2;

FIG. 15 is a graphical representation of the data in Table 5 for theZeta Potential v. pH of Particle 3;

FIG. 16 is a graphical representation of the data in Table 6 for theZeta Potential v. pH of Particle 6; and,

FIG. 17 is a graphical representation of the data in Table 7 for theZeta Potential v. pH of the Pigments.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to thefollowing detailed description of illustrative and preferredembodiments. It is to be understood that the scope of the claims is notlimited to the specific compositions, methods, conditions, devices, orparameters described herein, and that the terminology used herein is notintended to be limiting of the claimed invention. Also, as used in thespecification, including the appended claims, the singular forms “a,”“an,” and “the” include the plural, and reference to a particularnumerical value includes at least that particular value, unless thecontext clearly dictates otherwise. When a range of values is expressed,another embodiment includes from the one particular value and/or to theother particular value. Similarly, when values are expressed asapproximations, by use of the antecedent basis “about,” it will beunderstood that the particular values form another embodiment. Allranges are inclusive and combinable.

Wireless communications between devices and between components withindevices are known to those skilled in the art. The terms “wireless” and“wireless communications” shall mean the communication betweencomponents or devices that are accomplished by any of a variety of meansincluding, Wireless Local Area Networks (WLAN) and Wireless PersonalArea Networks (WPAN). WLAN networks use the IEEE 802.11 standards,typically known as WIFI, which is intended to replace high speed cablingwith wireless communications. WPAN networks use the Bluetooth SpecialInterest Group standards, which are intended for wireless communicationbetween portable equipment or fixed equipment (for example a homethermostat) and its applications. Near Field Communication (NFC)technology is another suitable wireless communication tool usingstandards from, for example, the NFC Forum. The apparatuses and methodsof the present invention may also use wireless Radio FrequencyIdentification communication technology (RFID), with standards from anumber of regulatory bodies, including International Organization forStandards (ISO), International Electrotechnical Commission (IEC), ASTMInternational, DASH? Alliance and EPC Global. WPAN is also known as LAN(Local Area Networks) or WLAN (Wireless Local Area Networks), which is awireless computer network that links two or more devices using awireless distribution method within a limited area such as a home,school, office space, and the like. A piconet is a computer networkwhich links a wireless user group of devices using Bluetooth technologyprotocols. For example, a piconet could include an apparatus accordingto the present invention connected to a smart phone or a cell phoneconnected to a computer, a laptop and a Bluetooth-enabled sensor, forexample, a digital camera.

The term “frexel” is defined as a small pixel-like region of thekeratinous surface. A frexel might correspond to a small portion of afreckle or other skin feature, or it may correspond to an area of thekeratinous surface that does not have special features. The term frexelis used to suggest that what is being measured is on a 3-D surfacerather than a flat surface. A region of keratinous surface is comprisedof a plurality of frexels. For instance, if a resolution of 300 dots perinch (11.8 dots per mm or “dpmm”) is used, a frexel may have a width andheight of about 1/300th of an inch (0.085 mm) so that there areapproximately 90,000 frexels per square inch (about 140 frexels persquare mm). The surface of the human body may have millions of frexels.

All percentages and ratios used herein are by weight of the totalcomposition, and all measurements made are at 25° C., unless otherwisedesignated.

The methods, apparatuses, and compositions of the present invention arebest understood with reference to the method of use. Each of the processsteps, the apparatuses and the compositions used in that step aredescribed in turn below. The terms “device” and “apparatus” are usedinterchangeably throughout this specification.

Treatment Compositions

The present invention may utilize a variety of treatment compositions,for example, inks, dyes, pigments, adhesives, curable compositions,optically activated compounds (for example quantum dots), metal oxides(for example, TiO2), bleaching agents, texture reducing polymers, skincare compositions, hair colorants, hair removal compositions (oftenreferred to as depilatories), hair growth stimulants and mixturesthereof.

The treatment compositions of this invention can be delivered alone orin the presence of a dermatologically-acceptable carrier. The phrase“dermatologically-acceptable carrier”, as used herein, means that thecarrier is suitable for topical application to the keratinous tissue,has good aesthetic properties, is compatible with any additionalcomponents of the skin care composition, and will not cause any untowardsafety or toxicity concerns. Water is by far the most common carrier,and is typically used in combination with other carriers. The carriercan be in a wide variety of forms. Non-limiting examples include simplesolutions (water or oil based), emulsions, and solid forms (gels,sticks, flowable solids, amorphous materials). In certain embodiments,the dermatologically acceptable carrier is in the form of an emulsion.Emulsion may be generally classified as having a continuous aqueousphase (e.g., oil-in-water and water-in-oil-in-water) or a continuous oilphase (e.g., water-in-oil and oil-in-water-in-oil). The oil phase of thepresent invention may comprise silicone oils, non-silicone oils such ashydrocarbon oils, esters, ethers, and the like, and mixtures thereof.For example, emulsion carriers can include, but are not limited to,continuous water phase emulsions such as silicone-in-water,oil-in-water, and water-in-oil-in-water emulsion; and continuous oilphase emulsions such as water-in-oil and water-in-silicone emulsions,and oil-in-water-in-silicone emulsions. Additionally, the treatmentcomposition can include for purposes of proper formulation andstabilization anti-fungal and anti-bacterial components.

The treatment composition comprises a dispersant, that can by apolyacrylate and derivatives thereof, for example poly methacrylate. Thecounter ion is preferably sodium, although potassium, ammonium and thelike are acceptable alternatives. The dispersant typically has amolecular weight of from about 1,000 to about 20,000, as measured bystandard GPC or NMR methodology known to those skilled in the art.Suitable dispersants include Darvan 811D, which is a sodium polyacrylatedispersant used in many of the Examples below, and Darvan 821A, which isan ammonium polyacrylate having a MW of about 3500.

The treatment compositions of the present invention may further comprisehumectants as a carrier or chassis for the other components in thetreatment composition. An exemplary class of humectants is polyhydricalcohols. Suitable polyhydric alcohols include polyalkylene glycols andalkylene polyols and their derivatives, including propylene glycol,dipropylene glycol, polypropylene glycol, polyethylene glycol andderivatives thereof; sorbitol; hydroxypropyl sorbitol; erythritol;threitol; pentaerythritol; xylitol; glucitol; mannitol; butylene glycol(e.g., 1,3-butylene glycol); pentylene glycol; hexane triol (e.g.,1,2,6-hexanetriol); glycerin; ethoxylated glycerine; and propoxylatedglycerine.

Other suitable humectants include sodium 2-pyrrolidone-5-carboxylate,guanidine; glycolic acid and glycolate salts (e.g., ammonium andquaternary alkyl ammonium); lactic acid and lactate salts (e.g.,ammonium and quaternary alkyl ammonium); aloe vera in any of its varietyof forms (e.g., aloe vera gel); hyaluronic acid and derivatives thereof(e.g., salt derivatives such as sodium hyaluronate); lactamidemonoethanolamine; acetamide monoethanolamine; urea; sodiumpyroglutamate, water-soluble glyceryl poly(meth)acrylate lubricants(such as Hispagel®) and mixtures thereof.

Inks, dyes, metal oxides and pigments (collectively referred to as“colorants” below) are used to modify the color or reflectance of thekeratinous surface. These compositions are commonly used to modify colorand reflectance in cosmetic, “make-up” compositions. Foundation,lipstick, eyeliner are just a few examples of these compositions, butthey are all applied evenly across large portions of the keratinoussurface, that is they are macro-applications. In sharp contrast, thepresent treatment compositions are selectively applied on a very smallscale to select areas, that is, a micro application. Suitable colorantsmay include inorganic or organic pigments and powders. Organic pigmentscan include natural colorants and synthetic monomeric and polymericcolorants. Organic pigments include various aromatic types such as azo,indigoid, triphenylmethane, anthraquinone, and xanthine dyes which aredesignated as D&C and FD&C blues, browns, greens, oranges, reds,yellows, etc. Organic pigments may consist of insoluble metallic saltsof certified color additives, referred to as the Lakes. Inorganicpigments include iron oxides, ferric ammonium ferrocyanide, manganeseviolet, ultramarines, chromium, chromium hydroxide colors, and mixturesthereof. The pigments may be coated with one or more ingredients thatcause the pigments to be hydrophobic. Suitable coating materials thatwill render the pigments more lipophilic in nature include silicones,lecithin, amino acids, phospholipids, inorganic and organic oils,polyethylene, and other polymeric materials. Suitable silicone treatedpigments as disclosed in U.S. Pat. No. 5,143,722. Suitable coatingmaterials that will render the pigments more hydrophilic in natureinclude silica, alumina, and polyethylene glycol triethoxysilanederivatives. Inorganic white or uncolored pigments include TiO2, ZnO,ZrO2, or semiconductor quantum dots, which are commercially availablefrom a number of sources. Other suitable colorants are identified inU.S. Pat. No. 7,166,279. Colorants are generally included at a weightpercent such that the skin care composition yields a perceptible color.In one embodiment, the skin care composition exhibits a color that isperceptibly different from the color of the applicator. By perceptiblydifferent, refers to a difference in color that is perceptible to aperson having normal sensory abilities under standard lightingconditions (e.g., natural illumination as experienced outdoors duringdaylight hours, the illumination of a standard 100 watt incandescentwhite light bulb at a distance of 2 meters, or as defined by CIE D65standard illuminate lighting at 800 lux to a 1964 CIE standardobserver).

Adhesives that are compatible with keratinous surfaces are known and anysuch adhesive can be applied with the apparatuses of the presentinvention. Commercially available adhesives compatible with keratinoussurfaces are available from the 3M Corporation of Minneapolis Minn. See,for example: U.S. Pat. No. 6,461,467, issued to Blatchford, et al.,filed on Apr. 23, 2001; U.S. Pat. No. 5,614,310, issued to Delgado, etal., filed on Nov. 4, 1994; and U.S. Pat. No. 5,160,315, issued toHeinecke et al., filed on Apr. 5, 1991. The entire disclosures of thesepatent applications are incorporated by reference. After the adhesive isselectively applied to the keratinous surface, a second treatmentcomposition can be dusted on the keratinous surface where it will stickto the adhesive. The second modification that is not adhered to thekeratinous surface can then be removed leaving behind a selective, microapplication of the second treatment composition. Likewise compositionsthat cure upon exposure to certain wavelengths of energy, infrared lightfor example, are known to the art and can be applied by the apparatusesof the present invention. By this method, the curable composition isselectively applied to the keratinous surface and then it is cured byexposing the keratinous surface to the curing energy source. The entirekeratinous surface can be exposed, or the exposure can be done at thesame time as the application.

Wrinkle or texture reducing polymers and skin tightening are known. See,for example: U.S. Pat. No. 6,139,829, issued to Estrin on Oct. 31, 2000;and US Patent Applications US20060210513A1, filed by Luizzi, et al. onMar. 21, 2005; US20070224158A1, filed by Cassin et al. on Mar. 18, 2005;and US20070148120A1, filed by Omura et al. on Jan. 14, 2005. The entiredisclosures of this patent and these published patent applications areincorporated by reference. More specifically, a cosmetic process forsoftening the wrinkles of wrinkled skin may comprise applying, to thewrinkled skin, a cosmetic composition, in particular an anti-wrinklecomposition, comprising, in a physiologically acceptable medium suitablefor topical application to the skin of the face: from 0.1 to 20% byweight of at least one tensioning agent, with respect to the totalweight of the composition.

Optically-activated particles can be used as or added to the treatmentcompositions of this invention. Sometimes referred to a “interferencepigments”, these particles include a plurality of substrate particlesselected from the group consisting of nylons, acrylics, polyesters,other plastic polymers, natural materials, regenerated cellulose,metals, semiconductor quantum dots and minerals; an optical brightenerchemically bonded to each of the plurality of substrate particles toform integral units in the form of optically-activated particles fordiffusing light. These particles help to reduce the visual perception ofskin imperfections, including cellulite, shadows, skin discolorations,and wrinkles. Each of the optically-activated particles are encapsulatedwith a UV transparent coating to increase the diffusion of light tofurther reduce the visual perception of the skin imperfections. Theencapsulated optically-activated particles are able to absorbultraviolet radiation and emit visible light; and the encapsulatedoptically-activated particles are able to both scatter and absorb lightin a diffuse manner in order to reduce the visual perception of skinimperfections, including cellulite, wrinkles, shadows, and skindiscolorations, when the optically-activated particles are applied tothe skin surface.

Hair colorants and hair removal compositions are also suitable for usewith the apparatuses of the present invention. Likewise, skin carecompositions can be applied with the apparatuses of this invention. Theskin care composition may be used as, for example, a moisturizer, aconditioner, an anti-aging treatment, a skin lightening treatment, asunscreen, a sunless tanner, and combinations thereof.

The skin care composition may comprise a safe and effective amount ofone or more skin care active (“active”) useful for regulating and/orimproving skin condition. “Safe and effective amount” means an amount ofa compound or composition sufficient to induce a positive benefit butlow enough to avoid serious side effects (i.e., provides a reasonablebenefit to risk ratio within the judgment of a skilled artisan). A safeand effective amount of a skin care active can be from about 1×10 ⁻⁶ toabout 25% by weight of the total composition, in another embodiment fromabout 0.0001 to about 25% by weight of the total composition, in anotherembodiment from about 0.01 to about 10% by weight of the totalcomposition, in another embodiment from about 0.1 to about 5% by weightof the total composition, in another embodiment from about 0.2 to about2% by weight of the total composition. Suitable actives include, but arenot limited to, vitamins (e.g., B3 compounds such as niacinamide,niacinnicotinic acid, tocopheryl nicotinate; B5 compounds, such aspanthenol; vitamin A compounds and natural and/or synthetic analogs ofVitamin A, including retinoids, retinol, retinyl acetate, retinylpalmitate, retinoic acid, retinaldehyde, retinyl propionate, carotenoids(pro-vitamin A); vitamin E compounds, or tocopherol, includingtocopherol sorbate, tocopherol acetate; vitamin C compounds, includingascorbate, ascorbyl esters of fatty acids, and ascorbic acid derivativessuch as magnesium ascorbyl phosphate and sodium ascorbyl phosphate,ascorbyl glucoside, and ascorbyl sorbate), peptides (e.g., peptidescontaining ten or fewer amino acids, their derivatives, isomers, andcomplexes with other species such as metal ions), sugar amines (e.g.,N-acetyl-glucosamine), sunscreens, oil control agents, tanning actives,anti-acne actives, desquamation actives, anti-cellulite actives,chelating agents, skin lightening agents, flavonoids, proteaseinhibitors (e.g., hexamidine and derivatives), non-vitamin antioxidantsand radical scavengers, peptides, salicylic acid, hair growthregulators, anti-wrinkle actives, anti-atrophy actives, minerals,phytosterols and/or plant hormones, tyrosinase inhibitors, N-acyl aminoacid compounds, moisturizers, plant extracts, and derivatives of any ofthe aforementioned actives. The term “derivative” as used herein refersto structures which are not shown but which one skilled in the art wouldunderstand are variations of the basic compound. For example, removing ahydrogen atom from benzene and replacing it with a methyl group.Suitable actives are further described in U.S. application publicationNo. US2006/0275237A1 and US2004/ 0175347A1.

Contrast Ratio

One method of characterizing the treatment compositions of the presentinvention is by its Contrast Ratio. Herein, “contrast ratio” refers tothe opacity of the treatment compositions of the present invention, orthe ability of the composition to reduce or prevent light transmission,determined after the composition is drawn onto an opacity chart (FormN2A, Leneta Company of Manwah, N.J. or the equivalent thereof), and byusing a spectrophotometer with settings selected to exclude specularreflection. The composition is diluted with a 1% Stabylen 30 in DI waterpremix at a 10:1 ratio. It is applied to the top of the opacity chartand then is drawn into a film having a thickness of approximately 0.01inches using a film applicator (e.g., as commercially available from BYKGardner of Columbia, Md., or the equivalent thereof). The film isallowed to dry for 2 hours under conditions of 22° C.+/−1° C., 1 atm.Using a spectrophotometer, the Y tristimulus value (i.e., the XYZ colorspace of the film) of the product film is measured and recorded. The Ytristimulus value is measured in three different areas of the productfilm over the black section of the opacity chart, and also in threedifferent areas of the product film over the white section of theopacity chart.

The contrast ratio for the treatment compositions of the presentinvention, is preferably from about 5 to about 35, more preferably fromabout 10 to about 30, and even more preferably from about 20 to about30.

The contrast ratio is calculated as the mathematical average of thethree Y tristimulus values over the black areas, divided by themathematical average of the three Y tristimulus values over the whiteareas, times 100:

${{Contrast}\mspace{14mu} {Ratio}} = {\frac{{average}\mspace{14mu} ({Yblack})}{{average}\mspace{14mu} ({Ywhite})} \times 100}$

EXAMPLES

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The examples are given solelyfor the purpose of illustration and are not to be construed aslimitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.

The following 10 Examples are all treatment compositions of the presentinventions. They can be applied by any of the methods and apparatusesdescribed herein, preferably, they are applied via a thermal ink jetprinter head and cartridge combination.

Example 1

% W/W Ingredient Description (as added) A WPG75PFSP 75% TiO2 Slurry inPropylene 22.50 Glycol/Water A WPG45GYSP 45% Iron Oxide Slurry Propylene3.30 Glycol/Water A WPG55GRSP 45% Iron Oxide Slurry Propylene 0.20Glycol/Water B Water Water 39.00 B Propylene Glycol Propylene Glycol12.50 B PVP/VA 735W 50% VP/VA Copolymer in water 1.50 B SymdiolHexanediol/Caprylyl Glycol 1.00 C Water Water 10.00 D Darvan 811D 5%Sodium Polyacrylate in water 10.00 Total 100.00To make the treatment composition of Example 1, first combineingredients of Phase A in an appropriate premix container. Add theingredients of Phase B into the main container. Mill using an IKA T25Tekmar mill at a low speed until mixture is homogenous. While milling,add Phase A to Phase B. Add Phase C (water wash) to the premix containerand add it to the main container while continuing to mill. Increasemilling to high speed and mill for 15 min. Add Phase D to the maincontainer while continuing to mill. Mill for an additional 2-3 minutesto ensure homogeneity then pour into a container, label, and store atambient conditions.

Example 2

% W/W Ingredient Description (as added) A WPG75PFSP 75% TiO2 Slurry inPropylene 22.50 Glycol/Water A WPG45GYSP 45% Iron Oxide Slurry Propylene3.30 Glycol/Water A WPG55GRSP 45% Iron Oxide Slurry Propylene 0.20Glycol/Water B Water Water 46.00 B Propylene Glycol Propylene Glycol12.50 B PVP/VA 735W 50% VP/VA Copolymer in water 1.50 B SymdiolHexanediol/Caprylyl Glycol 1.00 C Water Water 10.00 D Darvan 811D 5%Sodium Polyacrylate in water 3.00 Total 100.00To make the treatment composition of Example 2, first combineingredients of Phase A in an appropriate premix container. Add theingredients of Phase B into the main container. Mill using an IKA T25Tekmar mill at a low speed until mixture is homogenous. While milling,add Phase A to Phase B. Add Phase C (water wash) to the premix containerand add it to the main container. Increase milling to high speed andmill for 15 min. Add Phase D to the main container while continuing tomill. Mill for an additional 2-3 minutes to ensure homogeneity then pourinto a container, label, and store at ambient conditions.

Example 3

% W/W Ingredient Description (as added) A WPG75PFSP 75% TiO2 Slurry inPropylene 22.50 Glycol/Water A WPG45GYSP 45% Iron Oxide Slurry Propylene3.30 Glycol/Water B Water Water 55.59 B Propylene Glycol PropyleneGlycol 5.00 B PVP/VA 735W 50% VP/VA Copolymer in water 1.50 B SymdiolHexanediol/Caprylyl Glycol 1.00 C SIH RED No. 211P Iron Oxides C.I.77491 and Silica 0.11 D Water Water 10.00 E Darvan 811D 5% SodiumPolyacrylate in water 1.00 Total 100.00To make the treatment composition of Example 3, first combineingredients of Phase A in an appropriate premix container. Add theingredients of Phase B into the main container. Mill using an IKA T25Tekmar mill at a low speed until mixture is homogenous. While milling,add Phase C to Phase B. Increase milling to high speed and mill for 5min. Continue to mill and add Phase A to the main container (Phase B+C).Mill at high speed for 15 min. Add Phase D (water wash) to the premixcontainer and add it to the main container while continuing to mill. AddPhase E to the main container while continuing to mill. Mill for anadditional 2-3 minutes to ensure homogeneity then pour into a container,label, and store at ambient conditions.

Example 4

% W/W Ingredient Description (as added) A WPG75PFSP 75% TiO2 Slurry inPropylene 22.50 Glycol/Water A WPG45GYSP 45% Iron Oxide Slurry Propylene3.30 Glycol/Water B Water Water 48.09 B Propylene Glycol PropyleneGlycol 12.50 B PVP/VA 735W 50% VP/VA Copolymer in water 1.50 B SymdiolHexanediol/Caprylyl Glycol 1.00 C SIH RED No. 211P Iron Oxides C.I.77491 and Silica 0.11 D Water Water 10.00 E Darvan 811D 5% SodiumPolyacrylate in water 1.00 Total 100.00To make the treatment composition of Example 4, first combineingredients of Phase A in an appropriate premix container. Add theingredients of Phase B into the main container. Mill using an IKA T25Tekmar mill at a low speed until mixture is homogenous. While milling,add Phase C to Phase B. Increase milling to high speed and mill for 5min. Continue to mill and add Phase A to the main container (Phase B+C).Mill at high speed for 15 min. Add Phase D (water wash) to the premixcontainer and add it to the main container while continuing to mill. AddPhase E to the main container while continuing to mill. Mill for anadditional 2-3 minutes to ensure homogeneity then pour into a container,label, and store at ambient conditions.

Example 5

% W/W Ingredient Description (as added) A WPG75PFSP 75% TiO2 Slurry inPropylene 22.50 Glycol/Water A WPG45GYSP 45% Iron Oxide Slury Propylene3.30 Glycol/Water B Water Water 30.59 B Propylene Glycol PropyleneGlycol 30.00 B PVP/VA 735W 50% VP/VA Copolymer in water 1.50 B SymdiolHexanediol/Caprylyl Glycol 1.00 C SIH RED No. 211P Iron Oxides C.I.77491 and Silica 0.11 D Water Water 10.00 E Darvan 811D 5% SodiumPolyacrylate 1.00 Total 100.00To make the treatment composition of Example 5, first combineingredients of Phase A in an appropriate premix container. Add theingredients of Phase B into the main container. Mill using an IKA T25Tekmar mill at a low speed until mixture is homogenous. While milling,add Phase C to Phase B. Increase milling to high speed and mill for 5min. Continue to mill and add Phase A to the main container (Phase B+C).Mill at high speed for 15 min. Add Phase D (water wash) to the premixcontainer and add it to the main container while continuing to mill. AddPhase E to the main container while continuing to mill. Mill for anadditional 2-3 minutes to ensure homogeneity then pour into a container,label, and store at ambient conditions.

Example 6

% W/W Ingredient Description (as added) A WPG75PFSP 75% TiO2 Slurry inPropylene 22.50 Glycol/Water A WPG45GYSP 45% Iron Oxide Slury Propylene3.30 Glycol/Water B Water Water 30.59 B Propylene Glycol PropyleneGlycol 30.00 B PVP/VA 735W 50% VP/VA Copolymer in water 1.50 B SymdiolHexanediol/Caprylyl Glycol 1.00 C SIH RED No. 211P Iron Oxides C.I.77491 and Silica 0.11 D Water Water 10.00 E Darvan 811D 5% SodiumPolyacrylate 1.00 Total 100.00To make the treatment composition of Example 6, first combineingredients of Phase A in an appropriate premix container. Add theingredients of Phase B into the main container. Mill using an IKA T25Tekmar mill at a low speed until mixture is homogenous. While milling,add Phase C to Phase B. Increase milling to high speed and mill for 5min. Continue to mill and add Phase A to the main container (Phase B+C).Mill at high speed for 15 min. Add Phase D (water wash) to the premixcontainer and add it to the main container while continuing to mill. AddPhase E to the main container while continuing to mill. Mill for anadditional 2-3 minutes to ensure homogeneity then pour into a container,label, and store at ambient conditions. pH was adjusted with 20% citricacid to 7.0-7.5.

Example 7

% W/W Ingredient Description (as added) A WPG75PFSP 75% TiO2 Slurry inPropylene 12.80 Glycol/Water A WPG45GYSP 45% Iron Oxide Slury Propylene16.00 Glycol/Water B Water Water 26.325 B Propylene Glycol PropyleneGlycol 30.00 B PVP/VA 735W 50% VP/VA Copolymer in water 1.50 B SymdiolHexanediol/Caprylyl Glycol 1.00 C SIH RED No. 211P Iron Oxides C.I.77491 and Silica 0.11 D Water Water 10.00 E Darvan 811D 5% SodiumPolyacrylate 1.00 Total 100.00To make the treatment composition of Example 7, first combineingredients of Phase A in an appropriate premix container. Add theingredients of Phase B into the main container. Mill using an IKA T25Tekmar mill at a low speed until mixture is homogenous. While milling,add Phase C to Phase B. Increase milling to high speed and mill for 5min. Continue to mill and add Phase A to the main container (Phase B+C).Mill at high speed for 15 min. Add Phase D (water wash) to the premixcontainer and add it to the main container while continuing to mill. AddPhase E to the main container while continuing to mill. Mill for anadditional 2-3 minutes to ensure homogeneity then pour into a container,label, and store at ambient conditions.

Example 8

% W/W Ingredient Description (as added) A WPG75PFSP 75% TiO2 Slurry inPropylene 12.80 Glycol/Water A WPG45GYSP 45% Iron Oxide Slury Propylene16.00 Glycol/Water B Water Water 26.325 B Propylene Glycol PropyleneGlycol 30.00 B PVP/VA 735W 50% VP/VA Copolymer in water 1.50 B SymdiolHexanediol/Caprylyl Glycol 1.00 C SIH RED No. 211P Iron Oxides C.I.77491 and Silica 1.375 D Water Water 10.00 E Darvan 811D 5% SodiumPolyacrylate 1.00 Total 100.00To make the treatment composition of Example 8, first combineingredients of Phase A in an appropriate premix container. Add theingredients of Phase B into the main container. Mill using an IKA T25Tekmar mill at a low speed until mixture is homogenous. While milling,add Phase C to Phase B. Increase milling to high speed and mill for 5min. Continue to mill and add Phase A to the main container (Phase B+C).Mill at high speed for 15 min. Add Phase D (water wash) to the premixcontainer and add it to the main container while continuing to mill. AddPhase E to the main container while continuing to mill. Mill for anadditional 2-3 minutes to ensure homogeneity then pour into a container,label, and store at ambient conditions. pH was adjusted with 20% citricacid to 7.0-7.5.

Example 9

% W/W Ingredient Description (as added) A SIH TiO2 R250 TiO2, Silica,and Aluminum 18.05 Hydroxide A SIH Yellow No. Iron Oxides C.I. 77492 andSilica 0.40 602P A SIH RED No. 211P Iron Oxides C.I. 77491 and Silica0.00 B Water Water 55.55 B Propylene Glycol Propylene Glycol 12.50 BPVP/VA 735W 50% VP/VA Copolymer in water 1.50 B SymdiolHexanediol/Caprylyl Glycol 1.00 B Darvan 811D 5% Sodium Polyacrylate1.00 C Water Water 10.00 Total 100.00To make the treatment composition of Example 9, first combineingredients of Phase B into the main container. Mill using an IKA T25Tekmar mill at a low speed until mixture is homogenous. Increase millingto high speed and add ingredients of Phase A one at a time. Continue tomill and add Phase C to the main container. Mill at high speed for 15min. Mill for an additional 2-3 minutes to ensure homogeneity then pourinto a container, label, and store at ambient conditions.

Example 10

% W/W Ingredient Description (as added) A SIH TiO2 R250 TiO2, Silica,and Aluminum 9.60 Hydroxide A SIH Yellow No. Iron Oxides C.I. 77492 andSilica 7.20 602P A SIH RED No. 211P Iron Oxides C.I. 77491 and Silica1.37 B Water Water 55.83 B Propylene Glycol Propylene Glycol 12.50 BPVP/VA 735W 50% VP/VA Copolymer in water 1.50 B SymdiolHexanediol/Caprylyl Glycol 1.00 B Darvan 811D 5% Sodium Polyacrylate1.00 C Water Water 10.00 Total 100.00To make the treatment composition of Example 10, first combineingredients of Phase B into the main container. Mill using an IKA T25Tekmar mill at a low speed until mixture is homogenous. Increase millingto high speed and add ingredients of Phase A one at a time. Continue tomill and add Phase C to the main container. Mill at high speed for 15min. Mill for an additional 2-3 minutes to ensure homogeneity then pourinto a container, label, and store at ambient conditions.

A summary of the ten Examples is given in Table 1 below. Included inthis summary are the particulate types and concentrations, thedispersant type and level, the pH, particle size distribution, and theOpacity.

TABLE 1 Darvan 811D Darvan (as 811D PSD in nm Contrast Ex. PG added)(active) pH D10 D50 D90 Ratio WPG75 WPG45 WPG55 PFAP GYSP GRSP Ex. 122.50 3.30 0.22 12.5 10.0 0.50 8.41 303.6 466.9 796.6 26.8 Ex. 2 22.503.30 0.22 12.5 3.0 0.15 8.59 286.8 434.7 721.4 25.4 SIH WPG75 WPG45 REDPFAP GYSP No. 211P Ex. 3 22.50 3.30 0.11 5.0 1.0 0.05 8.20 249.7 374.3601.0 24.7 Ex. 4 22.50 3.30 0.11 12.5 1.0 0.05 8.30 250.1 374.8 603.925.8 Ex. 5 22.50 3.30 0.11 30.0 1.0 0.05 8.33 228.0 337.7 533.9 21.5 Ex.6 22.50 3.30 0.11 30.0 1.0 0.05 7.33 231.6 344.9 547.3 21.0 Ex. 7 12.8016.00 1.38 30.0 1.0 0.05 8.43 223.4 348.6 627.3 28.6 Ex. 8 12.80 16.001.38 30.0 1.0 0.05 7.28 286.0 447.8 809.1 27.7 SIH SIH SIH TiO₂ YellowRED R250 No. 602P No. 211P Ex. 9 18.05 0.40 0.00 12.5 1.0 0.05 7.47509.7 782.9 1326 19.9 Ex.10 9.60 7.20 1.38 12.5 1.0 0.05 7.87 547.2851.3 1436 25.6

Zeta Potential Measurements

Herein, “zeta potential” refers to the electrokinetic potential of thecomposition as measured by a NanoBrook ZetaPALS Potential Analyzer fromBrookhaven Instruments Corporation. It must be noted that the treatmentcompositions of the present invention may need to be diluted to achievean accurate measurement of the Zeta potential of the particles containedwithin the treatment composition. Accordingly, the particulateconcentration used to measure Zeta potential may or may not be differentthan the particulate concentration of the treatment composition. TheNanoBrook Zeta PALS utilizes phase analysis light scattering todetermine the electrophoretic mobility of charged, colloidalsuspensions. The samples were prepared as follows. Non-pigmented chasseswere made with 0, 0.05%, and 0.15% Darvan 811D (Sodium Polyacrylateparticulate suspending agent), respectively (1-3 and 18 in Table 2below). Their pH was adjusted to 5, 7, or 9 using citric acid or AMPUltra PC 2000. Using the individual raw slurries, additional formulawere made using 1% active solid loading, 5% propylene glycol, 1.0%Symdiol, 1.5% PVP/VA, and varying levels of Darvan 811D (4-17 and 19-21in Table 2 below). Zeta potential samples were prepared by dilutingformula 4-17 and 19-21 to 0.1 g/ml into unpigmented chassis 1, 2, 3 or18 that supports a pH of 5, 7, or 9. Zeta potential was measured on aNanoBrook ZetaPALS Potential Analyzer using the Smoluchowski zetapotential model with 5 runs and 10 cycles. After running a standard(BIZR3), the cells were loaded with 1 ml of zeta potential samplesolutions. Zeta potential was measured as a function of pH and plottedbelow.

To make the treatment compositions in Table 2, first combine ingredientsof Phase A into the main container. Mill on low speed until mixture ishomogenous. If adding Phase B, increase milling to high speed and addthe ingredients of Phase B into the main container. Mill at a high speedfor 15 minutes until mixture is homogenous. Add ingredient of Phase C tothe main container. Mill for an additional 2-3 minutes to ensurehomogeneity then pour into a container, label, and store at ambientconditions.

Below are the results of the Zeta potential measurements for the samplesin Table 2. The results are grouped by particle, with the correspondingcolumn number given for each data point in the raw data.

TABLE 3 Column 4 8 14 19 pH mV STDEV mV STDEV mV STDEV mV STDEV 5 −19.271.22 −35.21 1.59 −39.70 1.01 −33.63 1.14 7 −37.57 1.78 −52.70 1.60−49.15 1.84 −40.53 2.86 9 −30.49 0.67 −55.82 0.88 −52.20 1.80 −41.043.79

TABLE 4 Column 5 9 15 20 pH mV STDEV mV STDEV mV STDEV mV STDEV 5 −17.471.08 −25.03 0.81 −35.29 1.30 −24.36 1.54 7 −33.99 0.90 −48.37 1.54−51.86 0.88 −32.61 2.43 9 −24.84 1.37 −52.76 0.93 −52.49 1.32 −30.812.26

TABLE 5 Column 6 10 16 21 pH mV STDEV mV STDEV mV STDEV mV STDEV 5−12.56 0.48 −13.60 1.00 −19.30 1.28 −25.40 2.99 7 −27.59 2.97 −45.581.31 −45.26 1.60 −20.97 1.91 9 −21.97 0.69 −42.48 1.94 −45.48 0.68−36.20 2.03

TABLE 6 Column 7 13 17 pH mV STDEV mV STDEV mV STDEV 5 −7.38 0.42 −9.390.90 −8.91 1.40 7 −2.97 1.41 −15.37 0.58 −11.46 1.53 9 −4.50 1.48 −21.711.37 −15.87 0.93

TABLE 7 Column 11 12 13 pH mV STDEV mV STDEV mV STDEV 5 −7.79 0.99−10.74 0.66 −9.39 0.90 7 −11.42 0.71 −16.74 0.65 −15.37 0.58 9 −19.001.51 −30.79 1.05 −21.71 1.37

Tables 3-7 and the raw data graphed in these Tables, as shown incorresponding FIGS. 13-17, demonstrate a variety of conditions fromwhich the present invention is drawn. Specifically, the treatmentcompositions of the present invention preferably have a pH that fallswithin the range of 5-10. Further, these compositions have a Zetapotential of negative 20 or less, or greater than positive 20,preferably, negative 30 or less, or greater than 30. It is important tonote that zero on the zeta potential graph indicates no charge on theparticles. Thus, negative 20 and positive 20 represent particles witheither a negative charge or a positive charge of 20. Both positive andnegative charges are preferred over zero charge for the particles of thepresent invention. To be clear, it is desired to have the particlescharged, it is not important if the overall zeta potential is positiveor negative.

A particle size distribution D50 within the range of about 200 μm toabout 500 μm, and a D90 of less than about 1 μm is preferred. Asdescribed above, these preferred ranges were developed based on the rateat which particles settle out of the treatment composition, and the easewith which these particles could be moved back into solution aftersettling.

PSD Measurement

Herein, “PSD” refers to the particle size distribution of thecomposition as measured by a Horiba LA-950V2. The Horiba LA-950V2 LaserScattering Particle Size Distribution Analyzer uses the principles ofMie and Fraunhofer scattering theories for calculating the size anddistribution of particles suspended in a liquid. The range of particlesize measured is from 0.01 to 3000 μm on the LA950V2. Results arenormally displayed on a volume basis. The application of this method topigments has been developed using a flow cell procedure. Samples wereprepared by vortexing for 30 seconds with a Vortex Genie 2 to ensurethere is no residue in the bottom of the sample vial. 200 ml of DI waterwas added into the instrument and analyzed as a blank sample. Adisposable micro pipet was used to dispense enough sample into the DIwater in the instrument until the Transmittance was reduced from 100down to 90 +/−2%, approximately 250 μL. Results are reported as D10,D50, and D90 in Table 2.

Treatment Apparatuses

One example of how to use the treatment compositions of the presentinvention is in a device or apparatus to detect and modify tonalvariations on human skin. To better understand how the apparatuses ofthe present invention work, and why they are so beneficial to theconsumer, it is best to understand first what the device does. Thepresent methods, in their simplest form, are directed to analyzing andtreating tonal imperfections on human skin that comprises the steps oftaking at least one background image of at least 10 μm² of skin and thencalculating the average background L value of the image on a grey scale.Further, from the same image, a localized L value is calculated forindividual pixels or a group of pixels. The local L value is thencompared to the background L value to identify skin deviations. A skindeviation is an area of skin where the absolute value of the differencebetween a local L value and the background L, (this difference beingdefined as “ΔL_(M)” or the measured ΔL, “A” is commonly defined as thesymbol for a difference between two values) is greater than apredetermined ΔL_(S). The background L can be preset, or calculated by avariety of methods described below. The skin deviations are then treatedwith a treatment composition having a predetermined or variable contrastratio.

The background L can be calculated anywhere within the image. The imageis taken where the nozzles will fire the treatment composition. Thebackground L can be the arithmetic average, median, or mean of aplurality of local Ls, which means the calculation can include all ofthe local Ls in the image, or a subset thereof.

Likewise, there are provided apparatuses for treating human skin. Theapparatus has an applicator head that includes multiple applicatornozzles and a reservoir for containing a treatment composition, whichcan be a skin treatment composition. There is further provided a sensorand a CPU. The sensor takes an image of at least 10 μm² of skin and theCPU analyzes the image to calculate the average background L value. Thesensor output is also used to calculate the localized L value ofindividual pixels or groups of pixels of skin. The CPU then compares thelocal L value to the background L value to identify skin deviationswhere the difference between the two L values is greater than apredetermined value.

Exemplary treatment compositions for use with the present system includecosmetics, polymerics, aqueous, non-aqueous, particle loaded, opticalmodifier, fillers, optical matchers, skin actives, nail actives, hairactives, oral care actives, anti-inflammatory, antibacterial, surfactantor surfactant containing active, quantum dots and combinations thereof.Exemplary surfaces and substrates for the application of the treatmentcomposition by the present deposition system include keratinoussurfaces, woven surfaces, non-woven surfaces, porous surfaces,non-porous surfaces, wood, teeth, tongue, metallic, tile, fabric, andcombinations thereof

The central processing unit (“CPU”) of the device can be any of avariety of commercially available devices. In its simplest form, the CPUis a single programmable chip like those found in consumer electronicdevices such as a lap top computer, a cell phone, an electric razor andthe like. Those skilled in the art will know of a variety ofcommercially available chips and other processors suitable for use withthis invention. CPU may include Application Specific Integrated Circuit(ASIC), controller, Field Programmable Gate Array (FPGA), integratedcircuit, microcontroller, microprocessor, processor, and the like. TheCPU may also include memory functionality, either internal to the CPU ascache memory, for example Random Access Memory (RAM), Static RandomAccess Memory (SRAM) and the like or external to the CPU for example asDynamic Random-Access Memory (DRAM), Read Only Memory (ROM), Static RAM,Flash Memory (e.g., Compact Flash or SmartMedia cards), disk drives,Solid State Disk Drives (SSD) or even Internet Cloud storage. While itis anticipated that a remote CPU, either tethered to the device, orwhich communicates wirelessly, can be used to accomplish the methods ofthe present invention, a local CPU within the device is exemplifiedherein. Size and speed of the CPU is an important consideration of thedesign parameters, but cost and other considerations will be consideredby the device designers.

The predetermined ΔL_(S) is the absolute value of the difference betweenthe local L and the background L. This value, ΔL_(S), can be defined inabsolute numbers or as a percentage. The sensor is for example a camerathat takes black and white or color images, a spectrophotometer orsimilar devices that are sensitive to electromagnetic wavelengths. Theimages are taken, or converted to a standard grey scale that is known tothe art. It is understood that any numerical scale that measureslightness to darkness can be considered a “grey scale”. Moreover, asused herein, “grey scale” is intended to be a linear scale, or one band,or one visual attribute. For example, one “grey scale” visual attributecould be single wavelength or a narrow wavelength to define a specificvisual color. Another example of one “grey scale” visual attribute couldbe a mix of wavelength numerical values averaged for each pixel makingup the image, such as a true black, grey or white image from an RGBmixture.

It will also be understood to those skilled in the art that thebackground L value should not be too close to the ends of this scale.For example, if the grey scale is 0-100, with 0 being pure black and 100being pure white, a background in the 0-10 range, or in the 90-100 rangemay be too light or too dark to show meaningful differences.Accordingly, one can adjust the background lighting, or the gain on thecamera taking the image, to move the background L closer to the middleof the scale. In this example, a background L of 50 would be ideal, witha background L in the range of 10-90 preferred, 20-80 even morepreferred.

The most common grey scale is 0-255 (no units) other examples include0-1024 and 0-4096. In this example it would be desirable to use cameraand lighting settings that provide a background L value between 60 and210. Using the 0-255 gray scale the ΔL_(S) is preferably at least 0.5,more preferably at least 1 and even more preferably at least 1.5, toinitiate treatment of the skin. Likewise, ΔL_(S) can be measured as apercentage, for example, a numerical ΔL_(S) of 2.6 is approximatelyequal to 1.0% of a 255 grey scale. Thus ΔL_(S) may be plus or minus0.25%, preferably plus or minus 0.5% even more preferably plus or minus0.75%, of the grayscale.

The skin treatment compositions used to hide, or more appropriately, tocamouflage a skin deviation are described and exemplified in greaterdetail below. One important characteristic of the skin treatmentcompositions of the present invention is the contrast ratio. Thecontrast ratio of the treatment composition when treating the skin is atleast 0.1. The skin lightness and treatment composition lightness can bemeasured by a calibrated spectrophotometer using known methods. In thecase of using a calibrated spectrophotometer, the average L value ofhuman skin usually spans the range of about 25 to 75. In this case thecorresponding treatment composition has a lightness value of at least 2units greater, preferably at least 3 units greater, and even morepreferably at least 5 units greater than the average skin lightnessvalue of the consumer.

Images are taken in sequence or preferably continuously. A camera thattakes a minimum of 4 frames per second is preferred. Higher speedcameras (greater than 4 frames per second) are desired as well, forexample greater than 200 frames per second. All images are either takenin a grey scale or converted to a grey scale, the grey scale can haveany range, for example, 0-255, no units. This corresponds approximatelyto a refresh rate of 0.2 seconds or faster.

There is no technical difference between an image used for background Lvalues and those used for local L values, the difference is in theanalysis of the image. Hence, the images are continually sent to theCPU, that is, the processing unit, to calculate the L values, and ΔL_(M)values. By “sent” it is understood, that preferably at least 4 bits ofdata per pixel are transferred for each image, and preferably, this 4bit (or more) packet of data is used in the calculation of each local Lvalue. It is understood, that the background L can be calculated once ina treatment period and that value reused throughout the treatmentperiod. Or it can be continually recalculated as long as the treatmentprocess goes on. Moreover, there can be pre-programmed triggers toinitiate a recalculation of the background L. Also, the background L maybe retrieved from the CPU memory to be used for the current backgroundL. For example, if an extended period of time elapses and no skindeviations are found, or if skin deviations are being found toofrequently, a new background L might automatically be calculated.Likewise, ΔL_(S) can be a set value that remains constant throughout thetreatment cycle or it too can vary. ΔL_(S) can be reset during thetreatment cycle for any of a variety of reasons. If too many nozzles arefiring too frequently, the AL_(s) can be adjusted to lower the intensityof the nozzle firing. Similarly, if the nozzles are firing tooinfrequently, ΔL_(S) can be adjusted in the opposite direction toincrease the sensitivity of skin deviation detection. Those skilled inthe art will appreciate that modifying ΔL_(S) during treatment is amatter of programming the CPU to a desired algorithm.

When the ΔL_(M) exceeds the predetermined value, the skin deviation istreated with the treatment composition. Treatment requires firing one ormore of the nozzles which dispense the treatment composition onto theskin in the area of the skin deviation. Preferably the treatmentcomposition is applied to the skin deviations in a discontinuousdeposition pattern of discrete droplets between about 1 μm to about 100μm in size. It is also preferred that no more than 85% of the skindeviation is covered by the treatment composition. More specifically,the treatment composition is applied via a array of nozzles and thelocal L is calculated along the length of, and in the firing range of,the array of nozzles. The “array” can be a linear configuration,multiple rows, off-set, sine wave, curved, circular, or saw tootharrangements of nozzles. Those skilled in the printing arts willappreciate the various configurations of nozzle arrays that are possiblefor use in the methods and apparatuses disclosed herein. The “firingrange” of a nozzle will vary based on its size, type, the speed thedevice is moving, distance from the target, and other parameters.Examples of various types of nozzles suitable for use in the presentdevices are given below. But in general, “near the nozzle” as usedherein is meant to mean the image taken to calculate a local L value isclose to the area of skin where the treatment composition is depositedby the nozzle (the firing range, or landing zone of the nozzle). Withoutintending to limit the invention, near the nozzle means the image shouldbe taken within a radius of about 2 cm, preferably about 1 cm and evenmore preferably, about 0.7 cm from the center of the nozzle.

An individual nozzle may be fired to deposit the treatment composition,or multiple nozzles fired at the same time. The number of nozzles firedalong the linear array of nozzles can be adjusted based on the size ofthe ΔL_(M) and the size of the skin deviation. Furthermore the frequencyof nozzle firing can be adjusted based on the ΔL_(M), with more dropletsbeing fired in succession in response to larger ΔL_(M) values.

Firing intensity curves can be programmed into the CPU to adjust thefiring rate of nozzles. For example, if ΔL_(M) is equal to or slightlygreater than ΔL_(S), then the adjacent nozzle is fired 1 time. If ΔL_(M)increases to 2*ΔL_(S), then the adjacent nozzle is fired 25 times. Ifthe ΔL_(M) is 3*ΔL_(S), then the adjacent nozzle is fired 100 times.This non-limiting example is intended to show how the size of the ΔL_(M)with respect to the ΔL_(S) can determine the amount, and hence, theintensity of the firing of the nozzles adjacent the skin deviation.Those skilled in the art will appreciate that plotting a firingintensity curve using 2, 3 or more data points, and then programmingthat firing intensity curve into the CPU are known techniques.

The methods and apparatuses used by the present invention can be brieflysummarized as follows. Referring now to FIG. 1, where analytical window10 is an area that comprises a sample of skin 12 and nozzle array 20.Nozzle array 20 contains individual nozzles that are off or not firing24, and individual nozzles that are firing 22. Skin deviations 30 and 31are shown underneath nozzle array sections 32 and 33. Background L iscalculated on and around skin area 12, skin area 14 is where local L₁ ismeasured and skin area 16 is where local L₂ is measured. Skin area 14 isunder nozzle array 20 but not within a skin deviation. Thus, theabsolute value of local L₁—background L (ΔL_(1M)) is less than thepreset threshold to initiate nozzle firing. The ΔL_(S) thresholdrequired to initiate nozzle firing is a variable and is dependent on thescale used. For example, in a case where the 0-255 gray scale isutilized then the ΔL_(S) threshold required to initiate nozzle firingwould commonly be a value of 2 or greater. Thus in the example shown inFIG. 1 the value of ΔL_(1M) is less than 2. Likewise, skin area 16 iswithin skin deviation 30, and the absolute value of local L₂—backgroundL (ΔL_(2M)) is greater than about 2. Thus the nozzles around skin areas24 and 14 are generally off, and the nozzles around skin area 16 aregenerally firing. To insure the nozzles do not clog with particles ordried treatment composition, any nozzle can be fired at any time simplyto keep it clean and “healthy”. And as discussed above, the number ofnozzles directly over a skin deviation that are fired in response to theskin deviation can be adjusted based on the size of ΔL_(S), the size(e.g., surface area) of the skin deviation or other parameters devisedby those skilled in the art.

Treatment times will vary based on the size of the treatment area andthe precision and amount of the treatment. For example, a woman may wishto simply touch up a few small areas on her face before going to grocerystore. This treatment might take a few minutes. Alternatively, a youngbride might wear her wedding dress to a salon where a salon professionalmeticulously treats all exposed areas of skin prior to the wedding andthe taking of her wedding pictures. This full body treatment might takehours. Accordingly, the consumer will have tremendous control over theamount of time they choose to use the present device.

Referring now to FIG. 2, which shows a handheld apparatus 40 accordingto the present invention. The term “line” as used herein means a line,or method of communication between two elements. This line ofcommunication, for example, image capture line 48, can be a physicalconnection such as a hard wire or it can be a wireless communication asdescribed herein.

Apparatus 40 is directly above skin 18, separated by physical spacer 42.Physical spacer 42 has a set, predetermined height a such that when itcontacts skin 18, the mechanical and electrical elements above the skinare all at a known distance from the skin. The mechanical and electricalelements are associated with apparatus 40 and include, but may not belimited to, light 44, image capture device 46, nozzle array 20 which isembedded on cartridge die 54 which is attached to printer cartridge 52.All of these elements are enclosed within optional apparatus housing 41.Light 44 illuminates the area skin 18 within spacer 42 such that theimage capture device 46 has relatively constant illumination. Backgroundlighting will affect the image capture as portions of spacer 42 lift offof skin 18 and allow background light in and the illumination from light44 to escape, but small deviations in illumination can be corrected forprovided light 44 provides a relatively constant backgroundillumination. Light 44 can be a light emitting diode (LED), incandescentlight, neon based or any other commercially available source ofillumination. Light 44 can have constant illumination or adjustableillumination. For example, an adjustable light source might be useful ifthe background illumination is excessively bright or dark.

Image capture device 46 can be any of a variety of commerciallyavailable devices such as a simple camera or a digital cmos camera chip.Image capture device 46 takes a picture of skin 18 and sends it toprocessor 50 via image capture line 48 for analysis. Processor 50 isgenerally referred to as a central processing unit, or CPU, which maycomprise a simple circuit board, a more complex computer, or the likeand may include memory functionality. Those skilled in the art willappreciate that a CPU can be any of wide variety of commerciallyavailable programmable devices. As described above, the image may beanalyzed for local L values, background L values or both. Grey scaleconversion occurs within the analytical processing capabilities ofprocessor 50. The comparison of background L to local L to determine theΔL_(M) occurs within processor 50, which can be a commercially availableprogrammable chip, or other commercially available processing units.

Further provided is optional external CPU 43. External CPU 43 may be incommunication with any or all of the electronic components of theapparatus described herein. By way of example, external CPU 43 cancommunicate with CPU processor 50 via external CPU communication line 45and communicate with sensor 20 via sensor external communication line47. Lines 47 and 45 can be physical communication lines or, morepreferably, they are wireless communication lines.

The results of the image analysis, when compared to criteriapre-programmed into the processor, may result in a desired treatment ofthe skin. In such a case, for example when the calculate ΔL_(M) exceedsthe pre-determined ΔL_(S), a signal is sent from processor 50 tocartridge 52, via cartridge line 51, to fire one or more of the nozzlesin nozzle array 20. Power for cartridge 52, light 44, image capturedevice 46, processor 50, and other mechanical and electrical elementsthat might be present is supplied by power element 54 via multiple powerlines 55. Power element 54 can be turned off and on, which in turn turnsapparatus 40 off and on, via power switch 56 which can be locatedanywhere on apparatus 40 but is shown here on apparatus cover 58. Powerelement 54 may include energy storage functionality via a rechargeablebattery, a double-layer capacitor, a supercapacitor or a hybridbattery-capacitor system.

Turning now to FIG. 3 which is an exploded view of the cartridge 52comprising cartridge cap 62 and cartridge body 64. Body 64 includesstandpipe 66 which is typically enclosed within body 66 and definesnozzle outlet 68. Optional filter 70 helps keep excessively largeparticles, and other debris out of the nozzle array 76. Filter 70 andnozzle array 76 are on opposite sides of nozzle outlet 68. Treatmentcomposition 74 partially fills cartridge body 64. Foam core 72 fillscartridge 64 and helps to regulate back pressure of the treatmentcomposition 74. While a foam core cartridge is used to describe andexemplify back pressure can be regulated via bladders (not shown) andother methods known to the art, the foam core shown here is just oneexample of how to help regulate flow of the treatment composition 74 tostandpipe 66 through filter 70 and into nozzle array 76. Connector 78provides the electrical power and signal to nozzle array 76. Connector76 may be in wireless communication with the CPU processor 50, externalCPU 43, sensor 20 or any other electronic component of apparatus 40 andexternal apparatus associated therewith.

Treatment composition 74 within cartridge body 64 may comprise particlesand the treatment compositions preferably have a particle settling rateof less than 0.06 mm per day at 25° C. and 1 atm pressure. The treatmentcomposition may further have an elastic modulus between about 0.1 Pa toabout 1000 Pa at 25C and 1000 Hz. Preferably, the particles in thetreatment composition have a refractive index of between about 1.1 andabout 5.0.

Turning now to FIG. 7, which shows cartridge assembly 112 that has acartridge body 114 and a cartridge base 116, which collectively definecartridge reservoir 122. The size, shape and configuration of thecartridge assembly will vary based on the device in which it will beused. Cartridge assembly 112 is generally a rectangular box, but manyother configurations will be known to those skilled in the art and areall considered within the scope of the present invention. Die 126 isshown on one end of cartridge assembly 112. Die 126 contains nozzles 125and wiring (not shown) which are used to deposit treatment composition130 from the cartridge reservoir 122 to the surface being treated (notshown). While die 126 can be positioned anywhere on the exterior of thecartridge assembly 112, it is preferably adjacent standpipe 121.

Standpipe 121 is within cartridge reservoir 122 and is defined bystandpipe wall 124 and standpipe base 123. The volume within standpipe121 is standpipe reservoir 128. As discussed earlier, standpipe 121 anddie 126 are adjacent one another and share a common wall. Accordingly,standpipe wall 124 comprises a portion of die wall 127 of cartridge body114. The die/standpipe combination can be placed on any of the walls ofcartridge body 114 or even cartridge base 116. The volumetric ratio ofstandpipe reservoir 128 to cartridge reservoir 122 is discussed ingreater detail with respect to FIGS. 9-12.

A treatment composition pressure element 118 is shown in FIG. 7 as ablock of foam that fills a portion of cartridge reservoir 122. FIG. 8shows treatment composition pressure element 218 in cartridge reservoir222 of cartridge assembly 212. Treatment composition 130 (FIG. 7) fillscartridge reservoir 122 and flows through treatment composition pressureelement 118 because it is made of an open cell foam material know tothose skilled in the art. Alternatively, treatment composition 230 (FIG.8) fills only a portion of cartridge reservoir 222 because treatmentcomposition pressure element 218 is an impermeable membrane. Thepressure elements of the present invention can be open cell foam,bladders, flexible membranes, solid wax and the like.

Above and below treatment composition pressure element 118 are twounfilled portions of cartridge assembly reservoir 122 which are referredto herein as head spaces, specifically, in FIG. 7 standpipe head space132 and base head space 134. Both of these head spaces contain treatmentcomposition 130, which can be added to cartridge assembly 112 viaoptional treatment composition fill port 144 which is sealed withtreatment composition fill port plug 146. Fill port 144 and fill portplug 146 are often used in refillable cartridges, why cartridges thatare not intended to be refilled might be filled and then sealed withoutthe need for a fill port.

FIG. 8. shows treatment composition pressure element 218 as a flexiblemembrane situated between cartridge assembly base 216 and the other enddefined by standpipe 221 and die 226 comprising nozzles 225. Treatmentcomposition 230 occupies the area between treatment composition pressureelement 218 and standpipe 221, and there are no head spaces that containtreatment composition. This brings us to the discussion of treatmentcomposition dispersing devices 120 and 220 in FIGS. 7 and 8,respectively. In FIG. 7, treatment composition dispersing devices 120can be located in standpipe 121, or in standpipe headspace 132. In FIG.8, only one dispersing device 220 is shown and it is shown with mixingdrive 248.

Referring now to FIGS. 4, 5 and 6, which are photographs of the samefemale consumer. FIG. 4 represents her washed, natural, and uncoatedskin. FIG. 5 was taken after the subject applied makeup to her face in amanner she would normally do. FIG. 6 was taken after the consumer'smakeup was removed and her face treated with the apparatus and methodsof this invention. FIGS. 4, 5 and 6 are all taken on the same day, withno appreciable sun exposure between photographs (i.e. the consumer wasindoors for the entire treatment period).

Skin deviations 101, 102, 103 and 104 are clear in FIG. 4. After makeupis applied, skin deviations 101, 102, 103 and 104 are all still visible.There are tonal differences on the consumer's skin as well as the skindeviations of FIG. 5 vs. FIG. 4. It is clear from FIGS. 4 and 5 thatmakeup changes the overall tone of human skin, but does not cover upimperfections.

The consumer washes her face to remove the applied makeup after thephotograph of FIG. 5 is taken, and then her skin is treated with theapparatuses and methods of this invention, then the photograph of FIG. 6is taken. Skin deviations 101, 102 and 104 from FIGS. 4 and 5 arelargely invisible in FIG. 6. Skin deviation 103 is barely visible aftertreatment with the present apparatuses and methods. Accordingly, thepresent apparatuses and methods provide a substantial and visible changeto the appearance of human skin versus the natural condition of the skinand the skin with applied makeup.

Multiple configurations are shown for the dispersing devices of thepresent invention and others are contemplated for use with the presentinvention. Essentially, the dispersing devices are used to mix thetreatment composition within the limited space of the cartridge assemblyreservoir. The dispersing devices can be spherical balls, or irregularlyshaped objects. They can be plastic, metal, wood, or generally any othersolid, or semi-solid material. Preferably, the material does notdissolve in treatment composition, but even a dispersing device thatgradually dissolves could be used herein. The dispersing devices can befree floating as shown in FIG. 7, which relies on movement of the entirecartridge assembly to shake the dispersing elements and subsequently mixthe treatment composition. Likewise, the dispersing device can bemechanically moved as shown in FIG. 8, wherein treatment compositiondispersing device 220 is rotated by mixing drive 248. Dispersing device220 can be mechanically affixed to mixing drive 248 or magneticallyattached. Mixing drive 248 can rotate (as indicated by the arrows inFIG. 8), it can vibrate, or it can oscillate vertically and/orhorizontally.

An “L” shaped baffle 249 is shown in FIG. 8. Baffle 249 takes thetreatment composition 230 near and around dispersing device 220 andmixes it thoroughly. The flow of treatment composition 230 (shown bydirection flow arrows 250) immediately after being thoroughly mixed bydispersing device 220 and mixing drive 248 passes into standpipe 221. Bythis method of thorough mixing then immediately supplying the mixedtreatment composition to the standpipe, the treatment composition fed tonozzles 225 contains the proper blend of treatment particles and liquid.The general concept of using a baffle to direct the flow of mixedmaterial immediately to the standpipe, can be used with foam corepressure element as shown in FIG. 7 as element 118. Other combinationsof treatment composition pressure elements and baffles and dispersingdevices are contemplated for use in the present invention.

While numerous examples of how to impart mechanical mixing to thetreatment composition are shown, many others are contemplated within thescope of the invention, for example sonic mixing from either within thereservoir, or from a source exterior to the cartridge assembly. It isunderstood that the vast majority of prior treatment compositions didnot comprise particulate matter, thus mechanical mixing was neithernecessary nor desired.

Turning now to FIGS. 9-12, which show two different standpipes 321(FIGS. 9 and 10) and 421 (FIGS. 11 and 12). FIGS. 9 and 10 are twodifferent views of the same cartridge body 314 and cartridge reservoir322. Standpipe 321 defines a standpipe reservoir 328 which is defined bystandpipe wall 324 standpipe base 323. As discussed earlier, standpipebase is a portion of die wall 327 of cartridge body 314. Necessarily,the standpipe reservoir 328 has a volume that can be calculated bystandard methods, for example, base times height. Fluid can be used tofill the reservoir and the volume of that fluid measured or weighed, todetermine the standpipe volume. Those skilled in the art will befamiliar with many ways to determine both the volume of the standpipe aswell as the volume of the cartridge reservoir (322 I FIGS. 9 and 10). Toachieve the necessary and desired flow of particulate containingtreatment compositions through the nozzles of the present invention, theration of cartridge reservoir to standpipe reservoir, on a volumetricbasis is very important. Preferably, the ratio of the cartridgereservoir volume to the standpipe reservoir volume is from about 50:1 toabout 3:1, even more preferably from about 20:1 to about 4:1, and morepreferably about 8:1. Another way of characterizing the ratio of thecartridge volume to the standpipe volume is by the ratio of the surfacearea of the die wall to the standpipe base which is preferably fromabout 1.1:1 to about 3:1. FIGS. 11 and 12 are likewise are two differentviews of the same cartridge body 414 and cartridge reservoir 422.Standpipe 421 defines a standpipe reservoir 428 which is defined bystandpipe wall 424 standpipe base 423. As discussed earlier, standpipebase is a portion of die wall 427 of cartridge body 414.

While inkjet cartridges are shown and exemplified herein, treatmentcompositions may be applied with other “flow control” devices ornon-drop control devices. Flow control devices typically arecharacterized as “drop control techniques” where individual droplets ofthe substance are controlled. Ink jet printers, which are known to theart, are examples of drop on demand applicators and this technology isapplicable for use in the present invention. Piezo electric drop controldevices and other micro electromechanical systems are appropriate foruse with the current devices. Spray devices and electrostatic spraydevices are non-drop control techniques where droplets are produced andcontrolled only in aggregate. Often in a spray device, a lack ofindividual droplet control, or “randomness” is desired in order toproduce a smooth application over a relatively large area. By contrast,it is often desirable to provide very specific control of the amount andplacement of the treatment compositions.

Examples of drop control include “fine flow control” where the flow ofthe substance is precisely controlled to deliver droplets as desired;and “inkjet technologies.” An older inkjet technology includes supplyinga continuous flow of charged droplets past electrostatic deflectorplates which are alternately charged so that the plates either permit adroplet to pass or deflect to a gutter. This technique was the originaldesign basis for inkjet printers. Other inkjet technologies include“drop on demand” such as thermal devices provided by Hewlett Packard,and piezoelectric devices such as provided by Epson and other printermanufacturers. In one embodiment of the current invention, the drop ondemand technology is combined with charging the droplets.

Equipment that might be useful in constructing an apparatus of thepresent invention are described in the following published patentapplications: WO 2008/098234 A2, Handheld Apparatus and Method for theAutomated Application of Cosmetics and Other Surfaces, first filed 11Feb., 2007; WO 2008/100878 A1, System and Method for Applying aTreatment composition to Change a Person's Appearance Based on a DigitalImage, first filed 12 Feb., 2007; WO 2008/098235 A2, System and Methodfor Providing Simulated Images Through Cosmetic Monitoring, first filed11 Feb., 2007; WO 2008/100880 A1, System and Method for Applying AgentElectrostatically to Human Skin, first filed 12 Feb., 2007; US2007/0049832 A1, System and Method for Medical Monitoring and TreatmentThrough Cosmetic Monitoring and Treatment, first filed 12 Aug., 2005;and US 2007/0035815 A1, System and Method for Applying a Treatmentcomposition to Improve the Visual Attractiveness of Human Skin, firstfiled 12 Aug., 2005; All six applications filed by Edgar et al. Theentire disclosure of each of the six Edgar et al. applications isincorporated herein by reference.

The apparatuses of the present invention are preferably handheld but canbe tethered to a structure that moves the apparatus across thekeratinous surface to be modified. If handheld, the consumer wouldsimply move the apparatus across the keratinous surface to be treated.Optionally, multiple apparatuses can be configured in a stationarystructure wherein the consumer places the keratinous surface to bemodified and multiple readings and applications occur simultaneously orin sequence.

The treatment composition can be applied to the keratinous surface byscanning and applying at the same time while making multiple passes overthe surface. Several advantages result from using multiple passapplication. The process for multiple pass applications is to make apartial application of the treatment composition, then to scan again thearea of skin that has received the partial application. A furtherapplication of treatment compositions can be made, and still furthermultiple pass scanning and applications can be made to approach anaesthetic goal. Thus, the consumer can select the end point of thetreatment, i.e. the “aesthetic goal”, thus tailoring the treatment timeto individual needs and preferences. Attempting to make all correctionsin one treatment pass has been shown to overcorrect in certain areas.

It may be desirable for the apparatus to treat from about 1.0% to about10% of the keratinous surface that is read by the sensor with atreatment composition. And the applicator may apply the first treatmentcomposition in droplets having an average diameter of from about fromabout 0.1 μm to about 50 μm.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A stable, particulate containing, printercomposition comprising: a. one or more particulate suspending agents ina concentration of from about 0.1% to about 5%, by weight; b. one ormore particulate compositions, wherein the particles in the particulatecomposition have a combined Particle Size Distribution D50 in the rangeof about 200 μm to about 500 μm; and, c. water; and, wherein the one ormore particulate compositions has a zeta potential of negative 20 orless, or greater than positive 20, preferably, negative 30 or less, orgreater than
 30. 2. The treatment composition according to claim 1,wherein the particulate suspending agent is a polyacrylate orpolyacrylate derivative with a counter ion selected from the groupconsisting of sodium, potassium, ammonium and mixtures thereof,preferably the dispersant is sodium polyacrylate, and more preferablythe dispersant has a molecular weight of between about 1,000 and about20,000.
 3. The treatment composition according to claim 1, wherein theparticles are present in a concentration of from about 1% to about30.0%, by weight, and preferably the particles in the particulatecomposition have a combined Particle Size Distribution D90 of less thanabout 1 μm.
 4. The treatment composition according to claim 1, whereinthe particulate composition comprises TiO₂ particles and a secondparticulate composition which is an iron oxide based colorantparticulate composition, another colorant particulate composition, orboth.
 5. The treatment composition according to claim 1, furthercomprising one or more humectants in a concentration of from about 1.0%to about 50.0%, by weight, preferably the humectant comprisespolyethylene glycol in a concentration of from about 1.0% to about30.0%, by weight.
 6. The treatment composition according to claim 5,wherein the humectant is selected from the group consisting ofpolyethylene glycol, glycerin, butylene glycol, other glycols andmixtures thereof.
 7. The treatment composition according to claim 1,having a viscosity of from about 1 to about 100 centistokes.
 8. Thetreatment composition according to claim 1, wherein the particles in theparticulate composition are selected from the group consisting oftitanium dioxide, zinc oxide, aluminum hydroxide, iron oxides, boronnitride, silica, talc, carbon black and mixtures thereof.
 9. Thetreatment composition according to claim 1, wherein less than about 5%by volume of the particles in the particulate composition have a surfacetreatment that comprises silica.
 10. The treatment composition accordingto claim 1, which can be ejected from a thermal inkjet or piezo inkjetprinting system.
 11. The treatment composition according to claim 1,wherein the particles have an average settling rate of between about0.01 and 6.00 mm/year
 12. The treatment composition according to claim1, wherein the particles have a refractive index between 1.2 and 5.0.13. The treatment composition according to claim 1, wherein theparticles have a storage modulus of from about 0.1 mPa to about100 Pa.14. The treatment composition according to claim 1, wherein thecomposition has a pH in the range of from about 5 to about
 10. 15. Anapparatus for treating human skin, comprising: a. an applicator headcomprising one or more applicator nozzles; b. a reservoir comprising atreatment composition according to claim 1; c. a sensor; d. a CPU;wherein the sensor takes an image of at least 10 μm² of skin; the CPUanalyzes the image to calculate one or more localized L values ofindividual pixels or group of pixels; the CPU then compares the local Lvalue to a predetermined background L value to identify skin deviationswhere the difference between the background L value and the local Lvalue is greater than a predetermined ΔL_(S) value.
 16. The apparatus ofclaim 15, wherein the sensor is a camera capable of taking continuousimages at a rate of at least 4 frames per second.
 17. The apparatus ofclaim 15, wherein the background L is preselected by a user of thedevice, calculated from one or more images taken of the skin during atreatment cycle, or calculated for each image taken from pixels withineach image taken.
 18. The apparatus of claim 15, wherein the applicatorcomprises a thermal inkjet or piezo printer cartridge.
 19. The apparatusof claim 15, wherein the treatment composition comprises particles andhave a particle settling rate of less than 0.03mm per day at 25° C. and1 atm pressure, and an elastic modulus between about 0.1 Pa to about1000 Pa at 25 C. and 1000 Hz.
 20. The apparatus of claim 15, wherein thetreatment composition comprises particles which have a refractive indexof between about 1.1 and about 5.0.
 21. The apparatus of claim 15,wherein the predetermined ΔL_(S) value is plus or minus 1.5%, preferablyplus or minus 1.0% even more preferably plus or minus 0.5%, of thebackground L.
 22. The apparatus of claim 15, wherein the contrast ratioof the treatment composition when treating the skin is at least 0.1 andthe treatment composition has a lightness value of at least 1.5%,preferably at least 1.0% even more preferably at least 0.5% greater thanthe background L.
 23. The apparatus of claim 15, wherein each image iseither taken in a grey scale or converted to a grey scale.
 24. Theapparatus of claim 23, wherein the grey scale has a range of about 0-255units.
 25. The apparatus of claim 15, wherein the predetermined ΔL_(S)value is greater than 3, preferably greater than 2 and more preferablygreater than
 1. 26. The apparatus of claim 15, wherein the treatmentcomposition is applied to the skin deviations after the skin deviationare identified.
 27. The apparatus of claim 26, wherein the treatmentcomposition is applied to the skin deviations in a discontinuousdeposition pattern of discrete droplets between about 1 μm to about 100μm in size.
 28. The apparatus of claim 26, wherein less than 85% of theskin deviation is covered by the treatment composition.
 29. Theapparatus of claim 15, wherein the skin deviation is treated with theskin treatment composition one or more times after the skin deviation isidentified until the difference between the background L and the local Lof the skin deviation is less than 1.5%, preferably less than 1.0%, evenmore preferably less than 0.5% of the background L.
 30. The apparatus ofclaim 15, wherein the treatment composition is applied to the skindeviations after the skin deviation are identified via a linear array ofnozzles and the local L is calculated along the length of, and in thefiring range of, the array of nozzles.
 31. The apparatus of claim 30,wherein an individual nozzle is fired to deposit the treatmentcomposition, and the number of nozzles fired along the linear array ofnozzles can be adjusted based on the size of the ΔL_(M) and the size ofthe skin deviation.